[too much to read; jump to summary]
So the first question I have is what is your backup plan for critical non-recoverable data? The often issue with backups; is just how often do you verify that the backups are good? This is where a set of external drives can be useful to do your backups, unplug the hardware and rotate between the external drives so you have a current backup and a somewhat older backup. I have noticed using the USB backup utility of theirs can fail in the backup; so if you are using this method, remember to eject the drive reboot the NAS and verify the backup.
What you described on converting the movies from hard media to media server can be reproduced. I did something like that for my music collection, and re-did it a few more times when size of media was not as critical as my ability to detect the loss of quality in music. And yes, that will be a royal pain in the butt....
Ideal world if the NAS dies without taking the drive(s); it would be nice to have a backup hardware. I found this out when my NAS took a dump on a firmware update. I bought another NAS box and the raid was back online within 10 mins of me inserting the old disks into the new raid. I returned the NAS to the MFG due to the failed flash and now have a backup NAS. I did have a few external drives that I backed up the critical data to so even if the drives were no longer readable on the new device I was not 100% toast.
The good thing about the the type of data stored on the NAS is that high speed access is not needed. You just need good access while streaming to your device. So mirror + stripping may not be needed. Now if you are doing heavy I/O on the device then yea, you want performance + mirroring.
Key items; new drives are not the same as the old drives; so you would not create on big pool with the hardware. If the two new drives are the same make / model you can mirror the drives into a secondary pool. Due to total amount of space used you are not hungry for space, so I would use the secondary pool as a backup to the primary pool and be done with it.
Another option is to split each 12T drive into 2 chunks and sort of mimic what you have done with your first setup. Another "odd" thought is that you can Split one of the new drives into 2 sections, don't mirror it and use it as is. The second drive could also be used as "offline" backups where you copy all the files to the drive, eject the drive and remove it from the machine. With a simple backup such as that; the ability to move that device to a new NAS or even computer can be done to recover the files.
So the existing pool will continue to be used, the secondary drive can be used to provide rapid backup within the device, the last 12T drive will be used sort of the same way; but can be removed out of the device (or kept in the raid but not electronically connected).
[summary]
Mimic what you have done for the 4 x4T drives with the new 2 x 12T drives with mirror only. Continue to use the 4x4T setup for speed and the 2x12T as backup.
The same as above; but use a soft mirror between the 2x12T drives using Synology's software to maintain the backup features between each pool. This way if something happens on the write to the device you have a backup. By soft mirror; I am saying that periodically you have a scheduled backup process where the data from one drive is copied to the other. This makes the drive easier to be pulled from on NAS and used in another NAS for data recovery.
If I was keen on performing copy of NAS to external drive; I would keep the size of the work pool to somewhat smaller size than the removable drive.
For my solution using my NAS I went with more devices is better and performed manual copies between devices. I even setup NAS software in a VM and migrate critical data from the NAS into the VM and power off the VM. I also use external hard drives and copy files from the NAS in a backup chain. These devices are sort of plan "B" or "C". I am working on a plan "D" by encrypting my data and using a cloud service on a very small subset of materials. This material should be just outlook PST file along with documentation that I just could not throw money at to regenerate the info. Why look at plan "D"; house fire.
The only big got-ya issue using complex mirror / stripping / backup drive pool is migrating you lose portability of taking the drives from one device and moving them into a new one. The simple solution to this problem is to copy data off the complex setup to an external media.